Sulfur trioxide-Trimethylamine

Bitumen Ionomers. Moisture-resistant asphalts (qv) have been prepared by reaction of metal oxides with acid-functionalized bitumens (75). Maleic anhydride or sulfur trioxide/trimethylamine complexes have been used successfully for introduction of acid groups into asphaltic bitumens. 

The methyne proton of tris(pyrazolyl)methane is sufficiently acidic to be removed by raBuLi, and the resulting reactive intermediate readily reacts with electrophiles. Klaui prepared two new anionic tripodal nitrogen water-soluble ligands (the lithium salts of tris(pyrazolyl)- and tris(3-tert-butylpyrazol)-methanesulfonic, Tpms and Tmps B" respectively) by addition of lithiated tris(pyr-azolyl)methane to a sulfur trioxide-trimethylamine complex (Scheme 25).146... 

Sulfur trioxide-Dioxane, 1126-1127 Sulfiir trioxide-Pyridine, 1127-1128 Sulfur trioxide-Trimethylamine, 1128 Sulfuryl chloride, 196,1106,1128-1131 Swamping catalyst effect, 32,33 Synthesis gas, 224 Syringic aldehyde, 430,1047... 

Deprotection and sulfation was achieved by reduction of the azide to the corresponding acetamide with thioacetic acid [75] to afford III.47 (Scheme 29). Subsequent de-levulinoylation followed by acetylation gave III.48 in 64% yield over two steps. Reductive opening of the bisbenzylidene acetals with sodium cyanobo-rohydride and acid [76] afforded III.49 in 51% yield and by-product III.50, formed by acetyl migration from C3 to C4 (31%). Sulfation of III.49 was carried out with the sulfur trioxide-trimethylamine complex to give III.51 in 92% yield. Deacetylation followed by hydrogenolysis provided the target tetrasaccharide III.52. 

The corresponding 6-O-sulfated derivative (III.58) was prepared as follows. Starting from disaccharide III.62, acetylation followed by hydrogenolysis unmasked the 6-OH to give the corresponding alcohol with no acetate migration observed. Subsequent sulfation and saponification afforded III.58 in 87% yield over three steps. Quantitative preparation of the 4,6-di-O-sulfated disaccharide III.59 was achieved by treatment of the diol III.63 with the sulfur trioxide-trimethylamine complex. Alternatively, sulfation of III.62 followed by hydrogenolysis unmasked the 6-OH and subsequent sulfation provided III.59 in 71 % yield. 

Sulfur trioxide trimethylamine complex. See Trimethylamine sulfur trioxide Sulisobenzone. See Benzophenone-4 Sulphadione. See 4,4 -Diaminodiphenyl sulfone Sulphamic acid. See Sulfamic acid Sulphanilamide. See Sulfanilamide Sulphanilic acid. See Sulfanilic acid Sulphonated Lorol Liquid MA, MR. See MEA-lauryl sulfate... 

Trimethylamine, anhydrous Trimethylamine, aqueous sol n.. See Trimethylamine Trimethylamine sulfur trioxide CAS 3162-58-1 EINECS/ELINCS 221-614-7 Synonyms Sulfur trioxide trimethylamine complex... 

The first anionomer has a sulphate end fimctionality similar to that of heparin. Heparin has been shown to be responsible for the binding of a magnitude of proteins in-vivo (5). To prepare the anionic moiety having sulphonic acid at both chain ends, the PTMC diol was employed as a nucleophile to the electrophilic sulfur trioxide trimethylamine complex, giving the PTMC disulphonate as a product. 

The first studies on the sulfation of organic compounds, amino acids, and proteins have shown that pyridine/sulfur trioxide complex (pyridine/S03 or pyridine/Cl S03H),168-721 concentrated sulfuric acid,173,74 sulfuric acid//V,A -dicyclohexylcarbodiimide,175,761 and chloro-sulfonic acid177 are the most efficient reagents for the sulfation of tyrosine. More recently, alternative methods based on dimethylformamide/sulfur trioxide complex (DMF/S03),152,781 trimethylamine/sulfur trioxide (Me3N/S03),1152,1531 pyridinium acetylsulfate,137,791 and pyr-idinium trifluoroacetylsulfate1801 have been proposed to minimize side reactions which are difficult to control for the chemical sulfation of tyrosine peptides. 

Sulfur trioxide reactivity can also be moderated through the use of S03 adducts. The reactivity of such complexes is inversely proportional to their stability, and consequendy they can be selected for a wide variety of conditions. Whereas moderating S03 reactivity by adducting agents is generally beneficial, the agents add cost and may contribute to odor and possible toxicity problems in derived products. Cellulosic material has been sulfated with SCT—trimethylamine adduct in aqueous media at 0 to 5°C (16). Sulfur trioxide—triethyl phosphate has been used to sulfonate alkenes to the corresponding alkene sulfonate (17). Sulfur trioxide—pyridine adduct sulfates oleyl alcohol with no attack of the double bond (18). 

Because phenolic compounds are easily sulfonated, their sulfation must be accomplished with milder sulfating agents, eg, complexes of sulfur trioxide or chlorosulfonic acid with trimethylamine, dimethylformamide, pyridine, or dimethylaniline, in anhydrous or aqueous medium below 100°C (86-89). 

Sulfonic acids. Complexes of sulfur trioxide have been used to introduce the SO3H group to organic molecules. For example, organolithium reagents are converted to sulfonic acids by the trimethylamine complex and the dioxane complex is useful for replacing a silyl... 

Dimethyl sulfoxide-Sulfur trioxide [1, 309, before references]. The combination of DMSO and sulfur trioxide, in the form of the pyridine complex, in the presence of trimethylamine oxidizes primary and secondary alcohols in good yield to aldehydes and ketones, respectively.55 The reaction usually is complete within minutes and the products are isolated by acidification and precipitation with water. The reagent also oxidizes allylic alcohols to the corresponding a,fi-unsaturated carbonyl compounds. One advantage over the DMSO-DCC method is that the elaborate purification required when dicyclohexylurea is a product can be dispensed with. Testosterone, with a 17/3-hydroxyl group, was oxidized toA -androstene-3,17-dione very rapidly the 17-epimer required a period of 35 min. 

Cooper and Falcone have used a similar system (2.16) to make diarylureas in lower yields.49 When acetic anhydride was used instead of the trimethylamine-sulfur trioxide complex, the yield dropped from 59 to 57%. 

SFe Sulfur(VI) fluoride, 1 121 SH2 Hydrc en sulfide, 1 111 SOBr2 Thionyl bromide, 1 113 SO2 Sulfur dioxide, 2 160 SO2CI2 S dfuryl chloride, 1 114 S02 N(CH3)3 Trimethylamine-sulfur dioxide, 2 159 SOs CsHsN Pyridine-sulfur trioxide, 2 173... 

Ethyl acid phosphate 2-Ethylhexyl phosphate Stearyl acid phosphate catalyst, synthetic ammonia Ferrous sulfate anhydrous catalyst, tan-accelerating preps. Riboflavin-5 -phosphate sodium catalyst, textile lubricants Butyl acid phosphate Ethyl acid phosphate 2-Ethylhexyl phosphate Stearyl acid phosphate catalyst, textile printing D-Gluconic acid catalyst, thermoplastics Benzene phosphinic acid catalyst, thermosets Trimethylamine sulfur trioxide catalyst, thermosetting resin finishing Zinc nitrate... 

Chlorophenol Trimethylamine sulfur trioxide sterilant, vapors 3-Propiolactone sterilizable equip. 

Aminopropane sulfonic acid Trimethylamine sulfur trioxide C3H9N6O4P Melamine phosphate C3H9N9... 

The sulfonation of polar organometallics with sulfur trioxide has only scarcely been investigated. Quite satisfactory results have been reported when alkyl-, 2-alkenyl-, or (het)aryllithiums, bearing or not functional groups, are treated with the trimethylamine complex of sulfur trioxide. Acidification provides the sulfonic acids RSO3H in a straightforward manner. 

---